JP3448896B2 - Manufacturing method of antibacterial agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to silver, copper, zinc, tin and water.
Silver, lead, iron, cobalt, nickel, manganese, arsenic,
Prevention of antimony, bismuth, cadmium and chromium
And specific metal ions having antibacterial and antialgal properties
Also relates to a method for producing an antibacterial agent comprising a phosphate compound
The antibacterial agent obtained according to the present invention includes various binders
As an antimicrobial composition, such as paint, mixed with
For fibers, films, paper, ceramics, plastics, etc.
Can be used as an antibacterial molded product by adding to the material
And what is possible. [0002] 2. Description of the Related Art Silver, copper, zinc, tin, mercury, lead, iron, copper
, Nickel, manganese, arsenic, antimony, bismuth
Ions such as copper, barium, cadmium and chromium
Fungal, antibacterial and antialgal metal ions (hereinafter referred to as antibacterial
For a long time)
In particular, silver ions have a disinfecting and bactericidal action.
It is widely used as an aqueous silver acid solution. However,
The above-mentioned antifungal, antibacterial or antialgal metal ions are
It is often toxic to the human body.
There are various restrictions on the disposal method, etc.
I was [0003] To exhibit fungicidal, antibacterial or antialgal properties
If a small amount of antibacterial metal acts on
In recent years it has become clear that it is sufficient to prevent mold and antibacterial
Or, as an antibacterial agent having anti-algal properties, an antibacterial metal ion
Based on cation exchange resin or chelate resin
Antibacterial agent and antibacterial metal ion as clay mineral, inorganic ion
Proposed inorganic antibacterial agent supported on exchanger or porous body
Have been. Among the above various antibacterial agents, inorganic antibacterial agents include
It is generally safer than organic ones and has an antibacterial effect
Long lasting fruits and excellent heat resistance
I have. As one of inorganic antibacterial agents, montmorillonite and
Of sodium ions in clay minerals such as
Antibacterial agent ion-exchanged between lukali metal ion and silver ion
However, this is because the skeleton structure of the clay mineral itself is poor in acid resistance.
Therefore, silver ions are easily eluted in acidic solutions, for example.
And there is no sustained antibacterial effect. Also, silver ions are heat and
Unstable to light exposure, immediately reduced to metallic silver
Lack of long-term stability, such as coloring
You. In order to increase the stability of silver ions,
Ion exchange of silver ion and ammonium ion for olilite
There is one that is supported by coexisting with
It has not reached a practical level and has not reached a fundamental solution
No. Furthermore, it has adsorptive properties as other inorganic antibacterial agents
There is an antibacterial agent that carries an antibacterial metal on activated carbon.
Physically adsorbing or adhering degradable antibacterial metal salts
When exposed to moisture, antimicrobial metal ions rapidly
It is eluted and has no sustained antibacterial effect. [0006] Recently, a special zirconium phosphate antibacterial
Ag carrying reactive metal ions_0.01H_0.95Li_0.04Zr
_Two(PO_Four)_Three And other antimicrobial agents have been proposed.
Is stable physically and physically, has long-term antifungal and antibacterial properties
It is known as a material that exerts its effect (JP-A-3-8390)
5). However, in Japanese Unexamined Patent Publication No. 3-83905,
The method of synthesizing the antimicrobial agent exemplified physically is a dry method,
In the method, a mixture of raw material powders is baked to produce zirconium phosphate.
And then pulverize it into fine powder
Can not uniformly carry antibacterial ions
Therefore, it has low productivity and uniform and fine particle size
Problems such as difficulty in obtaining antibacterial agents
You. [0007] SUMMARY OF THE INVENTION The present invention relates to an antibacterial agent
In harsh environments exposed to sunlight or high temperature atmosphere
Is almost completely non-colored, resists mold for a long time, and has antibacterial properties
For producing antibacterial agent capable of exhibiting anti-algal properties
The task is to provide [0008] Means for Solving the Problems The present inventors have set forth the above section.
As a result of intensive studies to solve the problem,
Firing a valent metal salt has a negative impact on chemical and physical stability.
Excellent, anti-fungal, anti-bacterial and anti-algal
It was found to be extremely effective in obtaining fungicides.
Ming has been completed. That is, the present invention
And alkali metal ions, alkaline earth metal ions and
At least one ion selected from ammonium ions
React with phosphate ions and tetravalent metal ions in the presence of
The tetravalent metal phosphate represented by the following general formula [1]
For salt, silver, copper, zinc, tin, mercury, lead, iron, Kovar
, Nickel, manganese, arsenic, antimony, bismuth
, Barium, cadmium and chromium
Step (1) for supporting at least one kind of metal ion and temperature
From step (2) firing at 500-1300 ° C
Which is represented by the following general formula [2].
Of the antimicrobial agent to be used. A_aM^Two _Two(PO_Four)_Three・ NH_TwoO [1] [A is an alkali metal ion, an alkaline earth metal ion,
Less selected from hydrogen ion and ammonium ion
Are one kind of ion (the ionic value is m), and M
^TwoIs a tetravalent metal, and n is a number satisfying 0 ≦ n ≦ 6.
And a is 1 / m. ] M¹ _bA_cM^Two _Two(PO_Four)_Three・ NH_TwoO [2] [M¹Is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
Nickel, manganese, arsenic, antimony, bismuth,
At least one selected from lium, cadmium and chromium
One kind of metal ion (the ionic value is 1);
Is alkali metal ion, alkaline earth metal ion, hydrogen
Ion and at least one selected from ammonium ions
One type of ion (the ionic value is represented by m);^TwoIs
A tetravalent metal, n is a number satisfying 0 ≦ n ≦ 6, b
And c are positive numbers satisfying lb + mc = 1. ] The starting compounds used in the present invention and their compounds
The manufacturing method and the like will be described in detail. ○ Phosphoric metal phosphate
Salt The starting compound used in the present invention is produced by a specific method.
A tetravalent metal phosphate represented by the following general formula [1]:
You. A_aM^Two _Two(PO_Four)_Three・ NH_TwoO [1] [A is an alkali metal ion, an alkaline earth metal ion,
Less selected from hydrogen ion and ammonium ion
Are one kind of ion (the ionic value is m), and M
^TwoIs a tetravalent metal, and n is a number satisfying 0 ≦ n ≦ 6.
And a is 1 / m. ] The compound represented by the general formula (1) is
Morphus or a crystalline compound belonging to the space group R3c.
Shows the compounds in which each constituent ion forms a three-dimensional network structure.
You. As the tetravalent metal phosphate used in the present invention,
Because of little discoloration upon exposure, crystalline compounds
preferable. A in the above general formula [1] is an alkali
Metal ion, alkaline earth metal ion, hydrogen ion and
At least one ion selected from ammonium ions
And alkali metal ions and alkaline earth metal ions.
Preferred specific examples of on include lithium, sodium, and potassium.
There are lium, magnesium and calcium. General formula
The preferred ion as A in [1] is tetravalent phosphate
Because of the stability of metal salts and the availability of them at low cost, hydrogen ion
Ion, lithium ion, sodium ion and ammonium
Hydrogen ion and sodium ion
Is a preferable ion. In the general formula [1], M^TwoIs four-valent
And preferred specific examples include zirconium and titanium.
And tin, and considering the safety of the compound, zirconia
And titanium are particularly preferred tetravalent metals. An ingredient of the tetravalent metal phosphate of the above general formula [1]
The following are examples. LiZr_Two(PO_Four)_Three (NH_Four) Zr_Two(PO_Four)_Three NaZr_Two(PO_Four)_Three KTi_Two(PO_Four)_Three H_0.10Na_0.90Zr_Two(PO_Four)_Three H_0.60Na_0.40Zr_Two(PO_Four)_Three The tetravalent metal phosphate according to the present invention has a particle size of
Phosphate ions and tetravalent metal ions
A so-called wet reaction in which water is reacted in water at normal pressure or under pressure
It is obtained by synthesis according to the formula method. When synthesizing by a wet method, in water,
Alkali metal ions, alkaline earth metal ions and anions
At least one ion selected from monium ions
To allow phosphate ions to react with tetravalent metal ions
You. Reacting phosphate ions with tetravalent metal ions
The alkali metal ions and
The alkaline earth metal ions and ammonium ions are
It is an ion that becomes the A ion in the general formula [1]. Anti
The compound used in the reaction is a compound having these ions.
The compound is not particularly limited as long as it is a compound.
Hydroxide, sulfate, nitrate, chloride, carbonate, carbonate
There are hydrogen salts, phosphates and borates. The reaction between phosphate ions and tetravalent metal ions
To react, simply react the compounds with these ions.
However, in order to accelerate this reaction,
-Containing compounds (tetravalent metal compounds) and carboxylic acids or
Is a mixture of the salt in advance [Raw material (A)]
Reacting with a compound having an ion [raw material (B)]
Is preferred. Preparation of raw material (A) The raw material (A) used in the above production method is tetravalent
For uniformly mixing a metal compound and a carboxylic acid or a salt thereof
First, an aqueous solution of a tetravalent metal compound and carboxylic acid or
It is preferable to prepare by mixing an aqueous solution of a salt of Cal
Preferred mixing ratio of boric acid or a salt thereof and a tetravalent metal compound
In the case of one equivalent of the tetravalent metal compound (equivalent to one tetravalent metal atom
1 equivalent of carboxylic acid or its salt per formula weight
(Molecular weight per one boxyl group).
Good. [0019] Four types which can be used in the above-mentioned production method.
As the valent metal compound, a water-soluble or acid-soluble compound is suitable.
A preferred tetravalent metal wherein the tetravalent metal is zirconium
Specific examples of the metal compound include zirconium nitrate and diacetic acid.
Ruconium, zirconium sulfate, basic zirconium sulfate
System, zirconium oxysulfate and zirconium oxychloride
Etc. The carboxylic acid or a salt thereof has a carboxyl group
Aliphatic polycarboxylic acids having two or more and salts thereof are preferred.
Preferred examples thereof include the following compounds. Immediately
Fats such as oxalic acid, maleic acid, malonic acid and succinic acid
Aliphatic dibasic acid, sodium oxalate, sodium hydrogen oxalate
Lium, lithium hydrogen oxalate, ammonium oxalate
Of aliphatic dibasic acids such as ammonium hydrogen oxalate
Aliphatic oxyacids such as salt, citric acid, tartaric acid, malic acid, etc.
And their salts. Of these, oxalic acid
Particularly preferred are the sodium and ammonium salts thereof.
Compound. Preparation of raw material (B) In the above production method, phosphoric acid or
It is preferable to prepare an aqueous solution containing the salt in advance.
No. Preferred phosphates are water-soluble or acid-soluble salts
Ammonium phosphate and alkali metal phosphate
There are salts, specific examples of which are sodium dihydrogen phosphate,
Disodium hydrogen phosphate, trisodium phosphate, phosphoric acid
Diammonium hydrogen phosphate, ammonium dihydrogen phosphate and
And dipotassium hydrogen phosphate. ○ of tetravalent metal ion to phosphate ion
Equivalent ratio (α) When mixing the raw material (A) and the raw material (B),
ON is equivalent to 0.4 to 4.0 equivalents of phosphate ion.
Preferably equivalent, more preferably 0.6 equivalent
-2.0 equivalents, most preferably 0.6-0.8 equivalents
And The equivalence ratio (α) is less than 0.4 or
When it is larger than 4.0, the phosphoric acid used in the present invention
Compounds with structures different from tetravalent metal salts may be formed.
You. ○ pH value By mixing the raw material (A) and the raw material (B),
Reacts and precipitates fine particles of tetravalent metal phosphate
Form a slurry. Then, the pH value of the reactant slurry
Is adjusted to 7 or less by adding an acid or an alkali.
Is preferred to obtain tetravalent metal phosphate having high crystallinity.
Preferably has a pH of 1 to 6, more preferably 2 to
6, and then subjected to a heating reaction. ○ Reaction temperature The reactant slurry is heated above 80 ° C. in the reaction vessel
Preferably, the heating is performed at a temperature of 95 ° C or higher.
Heating is desirable. When heated below 80 ° C,
A compound different from the tetravalent metal phosphate used in
If heated above 95 ° C
Crystallization proceeds in a short time. Higher temperature increases crystallization rate
Under normal pressure, 97 ° C to 100 ° C is more preferable.
More preferably, from 110 ° C. under pressure, that is, under saturated steam pressure
200 ° C. is more preferred. In this temperature range,
The crystallization is usually completed within 2 to 50 hours. The solid content concentration of the slurry of the reaction product The solid content concentration of the reactant slurry is determined by stirring the reactant slurry.
Considering the properties, a range of 15 wt% or less is preferable. ○ Separation, washing and drying Filter, decant, centrifuge and filter the product
-Known separations such as press and cross-flow filtration systems
After being separated from the liquid phase by means of washing and washing,
After drying, loosen this as necessary, and add tetravalent metal phosphate
obtain. Support and baking of antibacterial ions To obtain the antibacterial agent of the present invention,
The following steps (1) and
It is necessary to perform the processing of step (2). ・ Step (1): Silver, copper, zinc, tin, mercury, lead, iron, iron
, Nickel, manganese, arsenic, antimony, bismuth
, Barium, cadmium and chromium
At least one kind of metal ion is supported on tetravalent metal phosphate
Process. Step (2): A tetravalent metal phosphate is heated to a temperature of 500 to 130.
Baking at 0 ° C. Loading of antibacterial metal ions [Step (1)] Silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel
, Manganese, arsenic, antimony, bismuth, barium
, At least one selected from cadmium and chromium
All metal ions have antifungal, antibacterial and antialgal properties
Known as metal ions
In addition to its safety, silver ions are fungicidal, antibacterial and
Is particularly effective as a metal ion that can enhance
You. Suitable for supporting antibacterial metal ions on tetravalent metal phosphate
A preferred method is an ion exchange reaction.
That is, in an aqueous solution containing an appropriate concentration of antibacterial ions,
Immersing the tetravalent metal phosphate obtained as described above
By this, the tetravalent metal phosphate carrying antibacterial ions
obtain. The temperature of the aqueous solution at this time is in the range of 0 to 100 ° C.
The immersion time should be a few minutes to tens of minutes.
However, immersion may be continued for a longer time (for example, several hours).
No. An aqueous solution containing antibacterial metal ions and phosphoric acid
If a tetravalent metal salt is brought into contact, the antibacterial metal ion
By the ion exchange reaction with A ion in the general formula [1]
Irrespective of the concentration of the aqueous solution,
Bacterial metal ion can be supported on tetravalent metal phosphate
Antibacterial metal ions in tetravalent metal phosphate
Water containing antibacterial metal ions
Particular restrictions on the concentration of antimicrobial ions in solution
But not phosphoric acid in aqueous solution containing antibacterial metal ions
When adding a tetravalent metal salt, use a slurry of tetravalent metal phosphate
-The degree to which the concentration can be stirred smoothly, for example, 20 wt% or less
Is preferable. As described above, in the general formula [2]
The coefficient b can be adjusted arbitrarily, but the antibacterial agent prevents
In order to exhibit the antibacterial property and anti-algae property to a high degree, the coefficient b
It is preferable to increase the value of. The value of coefficient b is 0.00
If it is 1 or more, it has sufficient antifungal, antibacterial and antialgal properties
However, if the value of the coefficient b is less than 0.01, it is prevented.
It is difficult to exhibit mold, antibacterial and anti-algal properties for a long time
Considering that there is a risk of
It is more preferable that the value is not less than 01 and not more than 0.5.
No. Baking [Step (2)] This baking step involves adding antibacterial metal ions to the phosphate tetravalent metal salt.
Before supporting and after supporting antibacterial metal ions
Although it may be carried out in any case, the chemical and antibacterial agent
Antibacterial agent that improves physical stability and highly prevents discoloration
To obtain antibacterial metal ions
It is preferable to carry out the firing step after carrying. By passing through this baking step, the antibacterial agent
Significantly improved chemical and physical stability, no discoloration
An antimicrobial agent having extremely excellent weather resistance can be obtained. Ma
In addition, almost no water adhered before firing
Therefore, the workability of the resin is also improved. In this process,
Baking the tetravalent metal phosphate at 500-1300 ° C
And preferably 600-1000 ° C., more preferably
Preferably, firing is performed at 700 to 900 ° C. 500
When baked at temperatures below ℃, the chemical and physical
To fully demonstrate the effect of improving stability
When firing at a temperature higher than 1300 ° C.,
Decreased antibacterial properties or finely divided metal tetravalent metal phosphate
To obtain fine-particle antibacterial agents because they fuse together
There is a problem that becomes difficult. There are no particular restrictions on the firing time
No, usually by firing for 1 to 20 hours, sufficient of the present invention
The effect can be exhibited. Heating rate and cooling rate
There is no particular limitation on the firing furnace capacity, productivity, etc.
Can be appropriately adjusted in consideration of the above. ○ Supporting hydrogen ions To obtain an antibacterial agent with extremely excellent antibacterial properties and weather resistance,
An antibacterial metal ion is added to the tetravalent metal phosphate according to the present invention.
It is preferable that both carry hydrogen ions. phosphoric acid
When the tetravalent metal salt has an ammonium ion,
By performing the step (2), ammonium ion
Since hydrogen ions remain after thermal decomposition, it is converted to tetravalent metal phosphate
By performing the step (2) (firing step) of the present invention, hydrogen ions
A supported tetravalent metal phosphate can be obtained. this
Preferred firing conditions are as follows: temperature is 600 to 1100 ° C.
And the time is about 0.5-2 hours. On the other hand, when the tetravalent metal phosphate is ammonium
If you have no or very little,
A step of supporting hydrogen ions on a tetravalent metal acid salt (hereinafter, referred to as
Abbreviated simply to step (3). Is preferable to add
As a typical method, acid tetravalent metal phosphate
There is a method of immersion in a solution, etc.
The above-mentioned method of calcining a tetravalent metal phosphate having a
It is a highly productive method compared to the method. Phosphate tetravalent
Acidic solution immersed to support hydrogen ions on metal salt
Preferred specific examples of the liquid include water such as hydrochloric acid, sulfuric acid and nitric acid.
There is a solution. The acid concentration, temperature, and immersion time of the acidic solution
There is no limitation, but generally the higher the acid concentration and the higher the temperature
Can support hydrogen ions in a short time
Therefore, a preferable acid concentration is 0.1 N or more, and is preferable.
The treatment temperature is 40 ° C. or more, more preferably 60 ° C. or more and
The temperature is 100 ° C. or less, and the preferable immersion time is 10 minutes.
The time is more preferably 60 minutes or more. Step (3) is performed before, after, or after step (1).
May be any of the same as step (1).
It may be performed before or after (2). Process
The preferred order of performing (1) to step (3) is illustrated.
It is as follows. That is, [Step (1) → Step (2)
→ Step (3)], [Step (1) → Step (3) → Step
(2)], [Step (3) → Step (1) → Step (2)], etc.
It is. Specific examples of preferred embodiments of the process
It is as follows. First, the tetravalent metal phosphate by the wet method
Synthesize the salt. Immerse this in an acidic solution such as nitric acid
Yields a tetravalent metal phosphate supporting hydrogen ions
[Step (3)]. Next, this is immersed in an aqueous silver nitrate solution.
To form a tetravalent metal phosphate carrying silver ions
A salt is obtained [Step (1)]. Finally, add the tetravalent metal phosphate
Firing in the temperature range of 500 to 1300 ° C [Step
(2)], an antibacterial agent is obtained. The antibacterial agent obtained as described above is as follows:
It is a compound represented by the general formula [2]. M¹ _bA_cM^Two _Two(PO_Four)_Three・ NH_TwoO [2] [M¹Is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
Nickel, manganese, arsenic, antimony, bismuth,
At least one selected from lium, cadmium and chromium
One kind of metal ion (the ionic value is 1);
Is alkali metal ion, alkaline earth metal ion, hydrogen
Ion and at least one selected from ammonium ions
One type of ion (the ionic value is represented by m);^TwoIs
A tetravalent metal, n is a number satisfying 0 ≦ n ≦ 6, b
And c are positive numbers satisfying lb + mc = 1. The present invention
The following are specific examples of the antibacterial agent obtained in (1). Ag_0.005Li_0.995Zr_Two(PO_Four)_Three Ag_0.01(NH_Four)_0.99Zr_Two(PO_Four)_Three Ag_0.05Na_0.95Zr_Two(PO_Four)_Three Ag_0.2K_0.8Ti_Two(PO_Four)_Three Ag_0.05H_0.05Na_0.90Zr_Two(PO_Four)_Three Ag_0.05H_0.55Na_0.40Zr_Two(PO_Four)_Three And the same charge as silver ion charge per mole of compound
In each of the above equations, Ag is set to Z
n, Mn, Ni, Pb, Hg, Sn, or Cu
Compound. The antimicrobial agent obtained as described above has an average
Fine particles with a particle size of several μm or less, often 1 μm or less
Yes, stable against light exposure,
It does not cause any discoloration. In the manufacturing process
As is clear from the firing process, the present invention
The antibacterial agents used have extremely good heat resistance.
You. Further, no change in the skeletal structure is observed even in an acidic solution.
Therefore, processing and storage when obtaining various molded products, and furthermore,
As in the case of conventional antibacterial agents, when used, the heating temperature
Alternatively, there are no restrictions such as light-shielding conditions. The use form of the antibacterial agent obtained by the present invention
Is not particularly limited, and may be mixed with other components as appropriate according to the application.
Or can be combined with other materials. example
Powder, powder-containing dispersion, powder-containing particles, powder-containing coating
Material, powder-containing fiber, powder-containing paper, powder-containing plastic
, Powder-containing film, powder-containing aerosol, etc.
It can be used in the form, and if necessary, a deodorant,
Various additives such as flame retardants, anticorrosion, fertilizers and building materials, or
It can be used together with the material. The antibacterial agent obtained according to the present invention comprises silver ion
Fungi, fungi and fungi on which antibacterial metal ions such as
For algae, fungicide and antibacterial for any use
Properties and anti-algal properties can be exhibited, for example,
It can be used effectively for applications. Work clothes, medical
Clothing, medical bedding, medical equipment, sports clothing, bandages,
Fishing nets, curtains, carpets, underwear, air filters
Fibers such as paper; paper such as wallpaper; drainage baskets, resin cutting boards
Sunday sundries consisting of resin molded products such as kitchenware, etc .; food
Films such as packaging films, medical films, and synthetic leather;
Bacteria equipment wall paint, antiseptic paint, fungicide paint, etc .; agriculture
Powders such as soil for use; liquid compositions such as shampoo. [0039] Examples and Comparative Examples Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.
This will be described more specifically. In addition, the following examples and
In Comparative Example, composition analysis and weather resistance test of antibacterial agent
And an antibacterial test. The conditions are as follows
You. ○ Composition analysis Converting a tetravalent metal phosphate with silver ions into a small amount of hydrofluoric acid
After dissolving to prepare the test solution, silver and sodium in the test solution
The concentration was measured by the atomic absorption method. In addition, the
Monium ion concentration is determined by indophenol spectrophotometry.
Was measured. ○ Antibacterial test According to the standard method of the Japanese Society of Chemotherapy,
An antibacterial test against enterobacteria was performed, and the minimum inhibitory concentration (M
IC) was measured. ○ Weather resistance test In Example 1, Example 2, Example 3, and Comparative Example 1,
Uses an antibacterial agent as a commercially available polyethylene resin [Mitsui Petrochemical Co., Ltd.
High Density Polyethylene Powder (trade name High
ZEX 2100JP)] 10 weight parts per 100 weight parts
To prepare a plate having a thickness of 5 mm. these
The plate was subjected to a weather resistance test for 3 cycles (1
The cycle was performed by irradiating ultraviolet rays at 60 ° C for 1 hour,
%, For 1 hour at 40 ° C. ), Before the test
The subsequent color was measured by a colorimeter and evaluated. Example 4-
6 and Comparative Examples 2 to 4, the pre-
To evaluate the discoloration of the sheet with high sensitivity
Therefore, the content ratio of the antibacterial agent and the thickness of the plate were changed.
And 100 parts by weight of the same commercially available polyethylene resin as above.
3mm thick plate containing 5 parts by weight antibacterial agent
Was prepared. Regarding the various antibacterial plates produced,
Using the UC-1 weathering tester manufactured by Yosei Machine Co., Ltd.
A three-cycle weathering test was performed (test using UC-1).
One cycle of the test conditions was 2 hours, 350 ° C at 60 ° C.
1 hour process of irradiating ultraviolet light of nm or less and wet at 40 ° C.
Starting from a one-hour process in an atmosphere of 95% or more.
You. ). Colors before and after the test are made by Nippon Denshoku Industries Co., Ltd.
Measured using a color difference meter SZ- # 80,
(ΔE) was determined.     ΔE = ｛(L₀-L₁)^Two+ (A₀-A₁)^Two+ (B₀-B₁)^Two｝^1/2             L₀, A₀, B₀: Color before test             L₁, A₁, B₁: Color after test Reference Example 1 (Formulation of K-type zirconium phosphate)
Made) Stir an aqueous solution of zirconium oxychloride (0.2 mol)
While adding oxalic acid (0.1 mol),
Phosphoric acid (0.3 mol) (phosphate ion 1)
The equivalent of zirconium ion per equivalent is 0.67).
The pH of the reaction solution was adjusted to 3.5 with an aqueous potassium hydroxide solution,
After heating under reflux at 5 ° C for 20 hours, the precipitate was filtered, washed with water, and dried.
And network zirconium potassium phosphate [KZr_Two(P
O_Four)_Three・ 1.2H_TwoO] (average particle size: 0.4 μm).
m). Reference Example 2 (NH_FourType zirconium phosphate
Preparation) Stir an aqueous solution of zirconium oxychloride (0.2 mol)
While adding ammonium chloride (0.1 mol)
Oxalic acid (0.1 mol) is added and phosphoric acid (0.3
Mol). Adjust the pH of the reaction solution with aqueous ammonia
After adjusting to 4.0 and heating at 95 ° C. for 48 hours under reflux, the precipitate
Is filtered, washed with water, dried and reticulated zirconium phosphate
Monium [NH_FourZr_Two(PO_Four)_Three・ 1.1H_TwoO]
(Average particle size: 0.7 μm). Reference Example 3 (Na-type zirconium phosphate salt)
Preparation) Stir an aqueous solution of zirconium oxychloride (0.2 mol)
While adding oxalic acid (0.1 mol),
Then, phosphoric acid (0.3 mol) is added. Caustic soda aqueous solution
The pH of the reaction solution is adjusted to 3.5 with 95 ° C. for 10 hours.
After heating to reflux, the precipitate was filtered, washed with water, dried, and
Sodium zirconate [NaZr_Two(PO_Four)_Three・
1.1H_TwoO] (average particle size: 0.8 μm). Embodiment 1 Powder of Na-type zirconium phosphate prepared in Reference Example 3
Was prepared by dissolving only a predetermined amount of silver nitrate without containing nitric acid.
After adding to the aqueous solution and stirring at 60 ° C. for 10 hours,
After the rally was filtered, it was sufficiently washed with pure water. In addition, 1
After heating and drying at 10 ° C overnight, 800, 90
After firing at 0 or 1000 ° C. for 4 or 10 hours,
The lumps of the fired material were loosened. Thus,
Thus, three kinds of antibacterial agents having the following composition were obtained. Ag_0.16Na_0.84Zr_Two(PO_Four)_Three Weather resistance for each of the above antibacterial agents obtained by firing under various conditions
As a result of performing the weatherability test, L values before and after the weather resistance test were shown.
As can be seen from Table 1, all antibacterial agents have excellent weather resistance.
I was In addition, as a result of the antibacterial test,
The growth inhibitory concentration (MIC) was 12 for all antibacterial agents.
It was 5 ppm. [0047] [Table 1] Embodiment 2 NH prepared in Reference Example 2_FourType zirconium phosphate salt powder
The powder is added to an aqueous solution in which a predetermined amount of silver nitrate is dissolved,
After stirring at 10 ° C. for 10 hours, the slurry was filtered,
Washed thoroughly with pure water. In addition, heat dry at 110 ° C overnight.
The following phosphate compounds obtained by drying Ag_0.16(NH_Four)_0.84Zr_Two(PO_Four)_Three At 800, 900 or 1000 ° C for 4 hours in a firing furnace.
After sintering, loosen the massive sinter using a crusher,
Thus, three kinds of antibacterial agents having the following composition were obtained. Ag_0.16H_0.84Zr_Two(PO_Four)_Three Weather resistance for each of the above antibacterial agents obtained by firing under various conditions
As a result of performing the weatherability test, L values before and after the weather resistance test were shown.
As can be seen from Table 2, all antibacterial agents have excellent weather resistance.
I was In addition, as a result of the antibacterial test,
The growth inhibitory concentration (MIC) was 12 for all antibacterial agents.
It was 5 ppm. [0049] [Table 2] Comparative Example 1 The following phosphate compound obtained in the same manner as in Example 2 was calcined.
As a result of performing the weather resistance test without
L value is 68, L value after weather resistance test is 28,
Coloring was observed. Ag_0.16(NH_Four)_0.84Zr_Two(PO_Four)_Three In addition, as a result of the antibacterial test,
The degree (MIC) was 125 ppm. Embodiment 3 A zirconium phosphate salt obtained in Reference Example 2 was fired in a firing furnace.
For 4 hours at 800, 900 or 1000 ° C
After immersing each in an aqueous silver nitrate solution, washing with water and drying,
Three kinds of antibacterial agents having the following composition formulas were obtained. Ag_0.16H_0.84Zr_Two(PO_Four)_Three A weather resistance test was performed for each of the above antibacterial agents after the baking process.
Table 3 below shows the L values before and after the weather resistance test.
As can be seen, all antibacterial agents have excellent weather resistance.
Was. In addition, as a result of the antibacterial test,
The static concentration (MIC) is 125p for all antibacterial agents.
pm. [0052] [Table 3]Embodiment 4 Powder of K-type zirconium phosphate prepared in Reference Example 1
And Na-type zirconium phosphate prepared in Reference Example 3
Is added to a 1N nitric acid solution containing silver ions,
Stirred at 60 ° C. for 10 hours. Then these slurries
After filtration, the product was sufficiently washed with pure water. In addition, 110 ° C
After heating and drying overnight at 750 ° C for 4 hours
The antibacterial agent was obtained from the antibacterial agent (the antibacterial agents of samples No. 1 and No. 3).
Agent). Embodiment 5 NH prepared in Reference Example 2 above_FourType zirconium phosphate
Is fired at 700 ° C. for 4 hours to obtain hydrogen.
Type zirconium phosphate [HZr_Two(PO_Four)_Three]
After that, this is added to a 1N nitric acid solution containing silver ions.
Then, the mixture was stirred at 60 ° C. for 10 hours. Then these sla
After the leach was filtered, it was sufficiently washed with pure water. In addition, 11
After heating and drying at 0 ° C overnight, bake at 750 ° C for 4 hours.
Thus, an antibacterial agent was obtained (sample No. 2 antibacterial agent). Embodiment 6 Of the Na-type zirconium phosphate prepared in Reference Example 3 above
Add powder to 0.1N nitric acid solution containing silver ions
Then, the mixture was stirred at 60 ° C. for 10 hours. Then these sla
After the leach was filtered, it was sufficiently washed with pure water. In addition, 11
After heating and drying at 0 ° C overnight, bake at 750 ° C for 4 hours.
Thus, an antibacterial agent was obtained (the antibacterial agent of Sample No. 4). Comparative Example 2 Of the Na-type zirconium phosphate prepared in Reference Example 3 above
Add powder to 1N nitric acid solution containing predetermined amount of silver nitrate
Then, the mixture was stirred at 60 ° C. for 10 hours. Then these sla
After the leach was filtered, it was sufficiently washed with pure water. Then, 11
Stop heating and drying overnight at 0 ° C, do not bake, antibacterial
An antibacterial agent was obtained (sample No. 5 antibacterial agent). Comparative Example 3 Hydroxyapatite [Ca_Ten(PO_Four)₆(OH)
_Two] Or zeolite A [composition: 0.94Na]_TwoO ・ A
l_TwoO_Three・ 1.92SiO_Two・ XH_TwoO^*], Silver nitrate
Alone or added to an aqueous solution of silver nitrate and ammonium nitrate,
After stirring at room temperature for 10 hours, wash thoroughly with water and
Drying gives antibacterial hydroxyapatite (flat
Uniform particle size: 1.2 μm) and antibacterial zeolite (average particle size)
(Diameter: 2.6 μm) (Sample Nos. 6 to 8 antibacterial)
(*: X = 1 to 4). Comparative Example 4 The antibacterial hydroxyapatite obtained in Comparative Example 3 (Sump
No. 6) and antibacterial zeolite (Sample No. 7)
Was fired at 750 ° C. for 4 hours (Sample No. 9,
10). The antibacterial agents prepared by the above method are shown in Table 4 below.
Was. [0059] [Table 4](Preparation and evaluation of antibacterial plate) Various antibacterials prepared in Examples 4 to 6 and Comparative Examples 2 to 4
As described in the evaluation conditions of weather resistance test
An antibacterial plate was prepared. These antibacterial plates
The results of the antibacterial test and weather test for
The results are shown in Table 5. [0061] [Table 5]As can be seen from the results in Table 5, the present invention
Antibacterial agents (Sample Nos. 1, 2, 3, 4) have antibacterial properties
Excellent weather resistance. On the other hand, zirconium phosphate
Even if the antibacterial agent has silver ions carried on the salt, the baking process
The sample that has not passed through (Sample No. 5) has a problem with weather resistance.
There is. In the case of antibacterial hydroxyapatite,
For the fired product (Sample No. 6), mold an antibacterial plate
Color immediately after firing, and there is also a problem with weather resistance.
Sample No. 9) has the problem of extremely low antibacterial properties.
You. In the case of antibacterial zeolite, unfired product (Sample No.
7 and 8) have a problem with the weather resistance, and the fired product (sample N
o. 10) is colored immediately after molding the antibacterial plate
In addition, there is a problem that the antibacterial property is extremely low. Embodiment 7 In 40 g of pure water, zirconium sulfate (0.12 mol), sulfuric acid
Ammonium acid (0.04 mol), phosphoric acid (0.18 mol
) And caustic soda (0.018) while mixing
Thus, a uniform aqueous solution was prepared. This reaction solution is heated to 120 ° C.
After heating under saturated steam pressure of 4 hours for 4 hours, the precipitate was filtered,
After washing and drying, a network zirconium phosphate is obtained.
Is added to a silver nitrate aqueous solution containing a predetermined amount of silver ions,
Stirred at 60 ° C. for 10 hours. Then these slurries
After filtration, the product was sufficiently washed with pure water. In addition, 110 ° C
After heating and drying overnight, baking at 900 ° C for 4 hours
Thus, an antibacterial agent having the following composition was obtained (sample No.
11 antimicrobial agents). Ag_0.15Na_0.05(NH_Four)_0.80Zr
_Two(PO_Four)_ThreeMethod for evaluating the antibacterial agent obtained in Example 4 and
Similarly, for the antibacterial agent of Sample No. 11 obtained above,
And evaluated the weather resistance and antibacterial properties, and the results are shown in Table 6 below.
Indicated. Comparative Example 5 Exactly the same as Example 7 except that it was not fired at 900 ° C.
Thus, an antibacterial agent (the antibacterial agent of Sample No. 12) was prepared.
In the same manner as in the method for evaluating the antibacterial agent obtained in Example 4,
The antibacterial agent of Sample No. 12 obtained in
The antibacterial properties were evaluated, and the results are shown in Table 6 below. [0066] [Table 6]As can be seen from the results in Table 6 above, phosphoric acid
Even when the zirconium salt is synthesized by the hydrothermal method,
By the formation, the weather resistance of the antibacterial agent can be improved. [0068] The antimicrobial agent obtained according to the present invention can be used in sunlight or
Even in a harsh environment where it is exposed to a high temperature atmosphere,
Almost no coloration, fungicidal, antibacterial and algae resistant
Extremely useful as a material that can demonstrate
It is.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-83906 (JP, A) JP-A-3-83905 (JP, A) JP-A-2-96508 (JP, A) JP-A-4-96 142349 (JP, A) JP-A-5-97414 (JP, A) JP-A-5-59308 (JP, A) JP-A-4-273803 (JP, A) JP-A-4-275370 (JP, A) JP-A-5-32512 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 1/00-65/02 C01B 25/00-25/46

Claims (1)

(57) [Claim 1] At least one ion selected from an alkali metal ion, an alkaline earth metal ion and an ammonium ion is present in water to form a phosphate ion and a tetravalent metal ion. With respect to the tetravalent metal phosphate represented by the following general formula [1] obtained by the reaction, silver, copper, zinc,
Step (1) of supporting at least one metal ion selected from tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium and chromium, and firing at a temperature of 500 to 1300 ° C. A method for producing an antibacterial agent represented by the following general formula [2], which comprises a treatment comprising a step (2). ^{_{A a M 2 2 (PO 4}} ) 3 · nH 2 O (1) [A represents an alkali metal ion, alkaline earth metal ions,
At least one type of ion selected from a hydrogen ion and an ammonium ion (the ionic value is represented by m);
² is a tetravalent metal, n is a number satisfying 0 ≦ n ≦ 6, and a is 1 / m. ] ^{_{M 1 b A c M 2 2}} (PO 4) 3 · nH 2 O [2] [M ¹ is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
A is at least one kind of metal ion selected from nickel, manganese, arsenic, antimony, bismuth, barium, cadmium and chromium (the ionic value is 1);
Is at least one kind of ion selected from an alkali metal ion, an alkaline earth metal ion, a hydrogen ion and an ammonium ion (the ionic value is represented by m), M ² is a tetravalent metal, and n is 0 ≦ n A number that satisfies ≦ 6, and b
And c are positive numbers satisfying lb + mc = 1. ]